• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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  • 优先权
    • 专利摘要:
    The present invention relates to an adsorbent article with reduced abrasion thanks to the immobility of its components, said article comprising zeolitic particles of at least one zeolitic adsorbent, said particles being immobilized with at least one resin, the average particle size of said less a zeolite adsorbent ranging from 0.03 mm to 3 mm, and the zeolite content being greater than or equal to 60% by weight. The invention also relates to a method for separating a fluid from one or more other fluids and / or separating a fluid from impurities contained in said fluid, comprising the step of bringing said fluid into contact with the fluid. at least one of said adsorbent article.
    公开号:FR3038240A1
    申请号:FR1556246
    申请日:2015-07-02
    公开日:2017-01-06
    发明作者:Sean Michael Stabler；Serge Nicolas；Guillaume Ortiz；Cecile Lutz；Stephane Kieger
    申请人:Carbonisation et Charbons Actifs CECA SA；
    IPC主号:
    专利说明:

    ARTICLE COMPRISING ZEOLITIC PARTICLES CONNECTED BY A
    RESIN
    The invention relates to an adsorbent article comprising particles of one or more zeolites and one or more clays, said particles being interconnected with one or more organic resins, such as polymers, especially polymers. thermoplastics. Said adsorbent has a high zeolite content, ensures rapid diffusion of fluids and allows better stability of the adsorbent because the abrasion between the particles is reduced or even avoided since the particles are immobilized in the article.
    [0002] US 2006/0166819 discloses resin-bound sorbents used as air conditioning and refrigeration drying devices. The sorbent is added in the form of a powder, e.g. ex. a zeolite powder, which is dispersed in a resin with injection or molding. The sorbent content is relatively low (from 25% by weight to 55% by weight) and the adsorption kinetics are very slow, resulting in a material that is not well suited when high adsorption and desorption kinetics are necessary.
    [0003] WO 2014/055546 improves the above disclosure by creating holes in the composite material to rapidly dispense the fluid to be dried and to increase the contact area between the fluid and the material. Absorption of moisture in the material takes place relatively slowly, as necessary. Such materials are expected to have low density and low volumetric capacity. Here again, the sorbent content is low (5% by weight to 55% by weight) and the adsorption kinetics remain slow.
    [0004] WO 2013/103433 discloses an article consisting of sorbents or catalytic beads connected to a substrate (film or thin sheet) with an adhesive, and wound in a spiral or arranged in a planar manner. The beads are regular adsorbents or catalysts. The article is provided as a catalyst or sorbent that is more effective for catalysis and adsorption due to a reduced pressure drop of the liquid or gas in the bed, compared to a packed bed. Such sorbent articles connected to a substrate are rather difficult to produce because of the plurality of components (sorbent, substrate and organic adhesive), and their resistance can be reduced, and there are risks of delamination or detachment of the sorbent from the substrate. substrate.
    US 2008/0148936 discloses composite structured adsorbents comprising a multi-channel frame consisting of ceramics, various inorganic oxides, and adsorbent materials. Each channel contains adsorbent particles that are not immobilized in the article, and abrasion readily occurs between said adsorbent particles.
    There is therefore still a need for adsorption articles (or adsorbent articles) having a high volumetric efficiency, with adsorption and desorption kinetics that are compatible, especially for uses for which kinetics of High adsorption is required, for example for the dynamic separation of gases and / or liquids, such as pressure swing adsorption (PSA), temperature modulated adsorption (TSA) and the like.
    There is still a need for zeolitic particles immobilized in adsorbent beds to prevent any movement of said particles, and thus avoid abrasion and dust formation, while maintaining a high separation efficiency (high volumetric capacity and kinetics). high).
    [0008] There is also a need for adsorbent articles (or blocks) with high zeolite content, low abrasion behavior between the particles, limited pressure drop and high diffusion kinetics.
    The Applicant has now discovered that the above needs can be satisfied in full or at least in part by the adsorbent article of the present invention, which will now be explained.
    According to a first embodiment, the present invention relates to an adsorbent article comprising zeolitic particles of at least one zeolitic adsorbent, said particles being immobilized with at least one resin, the average particle size of said at least one zeolitic adsorbent. ranging from 0.03 mm to 3 mm, preferably from 0.04 mm to 2 mm, more preferably from 0.05 mm to 1 mm, and the zeolite content being greater than or equal to 60% by weight, the zeolite content being more preferably greater than 70% by weight, preferably more than 80% by weight, more preferably strictly greater than 85% by weight, even more preferably strictly greater than 88% by weight, generally greater than or equal to 90% by weight, relative to the total weight of said article.
    In the present description, all numerical ranges include the upper and lower limits, unless otherwise indicated. In the present invention, "immobilized particles" means particles that exhibit reduced abrasion due to their immobility in the article and significant mechanical integrity to be self-supporting.
    The zeolite particles present in the article of the present invention may have various forms, for example beads, pellets, extrudates, crushed marbles, crushed pellets, flakes, cracked products, and in general all types of shapes, round or not, hollow or not, such as cenospheres as described in US 5856264, and the like, and / or mixtures thereof.
    According to a preferred embodiment, at least one zeolitic particle in the article has a dimension greater than or equal to 0.1 mm.
    Preferably, the zeolitic particles in the article comprise at least one zeolitic adsorbent in the form of one or more zeolites agglomerated with one or more inorganic binders, such as natural clays, synthetic clays or silica. , alumina and the like, preferably natural clays and / or synthetic clays, more preferably natural clays.
    It should therefore be understood that the expression "zeolite particles" comprises zeolitic adsorbents (agglomerates) and zeolite powder, the content by weight of the zeolite powder being less than 90% by weight, preferably less than at 70% by weight, more preferably less than 50% by weight, still more preferably less than 25% by weight, even more preferably less than 10% by weight and even more preferably less than 5% by weight, based on the total mass of the zeolitic particles. The weight ratio of the zeolite powder to the total mass of the zeolite particles is measured by sieving the zeolite particles after dissolution of the resin in a suitable solvent. The amount by weight of zeolite powder is the amount of zeolite particles passing through a 500 mesh screen (31 μm).
    The zeolite particles contained in the article of the present invention comprise at least one zeolite or a mixture of zeolites, which are advantageously chosen from zeolites A (LTA-type framework), chabazite (CHA-type framework), clinoptilolite (HEU type frame), ΙΈΜΤ (EMT type frame), ZSM-5 (MFI type cade), silicalite-1 (MFI type frame) and faujasite (FAU type frame), and more preferably, among zeolites of the FAU type.
    Among zeolites type FAU, zeolites X, MSX, LSX and Y, as well as mixtures of two or more of them in all proportions, are preferred. Zeolite X means a zeolite of FAU type, with a Si / Al molar ratio of between 1.15 and 1.50. Zeolite MSX (Medium Silica X) means a zeolite of the FAU type, with a Si / Al molar ratio of between 1.05 and 1.15. LSX zeolite (Low Silica X) means an FAU type zeolite with an Si / Al molar ratio of about 1.00 ± 0.05. Zeolite Y means a zeolite of FAU type, with a Si / Al molar ratio greater than 1.50.
    Among zeolites of MFI type, ZSM-5 zeolite means an MFI type zeolite with an Si / Al molar ratio greater than 10 and silicalite-1 zeolite means an MFI-type zeolite without aluminum.
    All the zeolites listed above are represented for example in Atlas of Zeolite Framework Types, fifth revised edition, 2001, ELSEVIER, published by the Structure Commission of the International Zeolite Association.
    The inorganic binder contained in the zeolitic particles is preferably chosen from kaolin, kaolinite, nacrite, dickite, halloysite, attapulgite, sepiolite, delaminated clays (for example in the form of gels), montmorillonites, bentonites, illites and / or metakaolins, as well as mixtures of two or more of them in all proportions.
    Examples of delaminated clays that are commercially available are, by way of illustration only, Min-U-Gel®, Pansil®, Pangel®, Cimsil®, Attagel®, Actigel®, etc. Such gels are described p. ex. in EP170299 or US6743745.
    The article of the present invention therefore comprises zeolitic particles which are immobilized with at least one resin. Examples of resins which are suitable for immobilizing the zeolite particles in the article of the present invention include polymers, especially thermoplastic homo- and / or copolymers, and also polycondensates. Nonlimiting examples of polymers include polyolefins, in particular low and / or high and / or ultra-high density polyethylene, polypropylene, ethylene copolymers, ethylene-vinyl acetate copolymers, polyacrylics, homopolymers and the like. and / or acrylonitrile copolymers, polyacrylates, polymethacrylates, acrylate copolymers and / or methacrylate copolymers, polystyrenes and / or styrene copolymers, polyesters, p. ex. polyethylene terephthalate, polybutylene terephthalate, halogenated polymers and copolymers such as polyvinylidene difluoride (PVDF) polymers, polymers and / or copolymers of polytetrafluoroethylene (PTFE), other fluoropolymers and homopolymers, polyamides, such as polyamide-11 and polyamide-12, as well as other even and odd polyamides, aromatic polyamides, as described in WO 2014/182861 and in WO 2014/055473, polyvinyl chlorides, polyurethanes polyethersulfones, polyetherketones, polycarbonates, epoxy resins, phenolic resins, thermosetting resins and elastomeric resins, and the like, and mixtures thereof.
    Preferred resins are those in the form of particles, preferably beads, agglomerates and bead aggregates having a preferred average particle size of less than 100 μm, preferably less than 50 μm, preferably less than 20 μm, more preferably less than 12 μm and more preferably less than 10 μm.
    As indicated above, the resins may be chosen from polymers and, in this case, the preferred polymers are those obtained by an emulsion polymerization process resulting in a small discrete particle size, generally ranging from 1 nm. at 100 μm, preferably from 1 nm to 50 μm, more preferably from 1 nm to 20 μm. The average particle size is measured using a MicrotracS3500 analyzer. The particles are mixed with deionized water and 1% Triton-X100 surfactant and sonicated before the test.
    Halogenated polymers are preferred, fluoropolymers are more preferred, and PVDF is even more preferred because they are compatible with zeolitic particles to form the articles of the invention.
    In the article of the present invention, the ratio between the particle sizes [(resin particle size) over (zeolite particle size)] is preferably from 1:20,000 to 3: 1, preferably from 1:10 000 to 2.5: 1, more preferably from 1: 1000 to 2: 1.
    Examples of resins may be organic adhesives or adhesive compositions or binding agents, such as adhesives, contact adhesives, pressure-sensitive adhesives, comprising one or more homo-and / or copolymers. thermoplastics and polycondensates listed above.
    As previously described, the article of the present invention has a high content of active material (ie adsorbent material), expressed as a zeolite content, which is greater than or equal to 60%. by weight relative to the total weight of said article, the zeolite content being preferably greater than 70% by weight, more preferably strictly greater than 80% by weight, even more preferably strictly greater than 85% by weight, of even more preferably more strictly greater than 88% by weight, generally greater than or equal to 90% by weight, relative to the total weight of said article.
    The quantitative amount of zeolite in the article is measured by X-ray diffraction, as explained below. This high content of adsorbent material makes it possible to obtain an article having a volumetric efficiency which is from 50% to 99% of the free adsorbent material, that is to say without resin.
    The resin content of the article of the present invention is measured by thermogravimetric analysis coupled with infrared spectrometry (TGA-IR). The analyzes are carried out for example in a METTLER Toledo TGA-DSC 2, coupled with a NICOLET ™ IR 6700 infrared spectrometer. The sample is heated under air from room temperature (25 ° C.) to 1100 ° C. with a fixed temperature gradient (usually 5 ° C per minute). The weight loss is recorded as a function of temperature and the exhaust gas produced is analyzed by IR, which makes it possible to calculate the resin content.
    According to another aspect of the present invention, the adsorbent article of the present invention may further comprise one or more additives. Nonlimiting examples of such additives may be chosen from rheology agents, pore-forming agents, processing aids, dispersing agents, lubricants, tackifiers, UV stabilizers, pigments, dyes, antioxidants, impact modifiers, phase change materials (PCMs), flame retardants, odorants and the like. According to one aspect of the invention, the adsorbent article may also comprise one or more compounds capable of changing color (color indicator) depending on the degree of adsorption of the zeolite (s). Such compounds are for example pigments, inks or dyes which react chemically while changing color (see WO 2006/079713 for examples of reactive inks).
    The adsorbent article may be formed by conventional machining techniques, such as injection molding, compression molding, extrusion and the like, as non-limiting examples. The process for preparing the article of the present invention generally comprises at least the following steps: a) mixing zeolitic particles with at least one resin in a homogeneous mixture; b) adding said homogeneous mixture to a machining device; c) shaping into the desired shape and size; d) applying enough heat to soften the resin; e) applying pressure to compress the particles to the desired density; f) the constant maintenance of the temperature and the pressure to allow the binding of the resin and the zeolitic particles; and g) cooling to hardening of the resin.
    The mixture can be made by frictional shear mixing to put the formulation in the form of a homogeneous matrix by hand or by mechanical means such as a ribbon blender. "Machining device" means any shaping device well known to those skilled in the art, and may, as non-limiting examples, be selected from an extruder, a compression molding machine, an injection molding machine and the like.
    [0034] The mold design for compression molding or the die for continuous extrusion requires a draft designed in the tool to allow simple extraction and transfer out of the forming tool. Such mold and tool designs are well known to those skilled in the art.
    The mixture of zeolitic particles with at least one resin obtained in step a) is also part of the present invention.
    The preferred resins used during the mixing in step a) above and which are present in the mixture of zeolitic particles according to the invention are those in the form of particles, preferably beads, agglomerates and aggregates of beads having a preferred average particle size of less than 100 μm, preferably less than 50 μm, more preferably less than 20 μm, more preferably less than 12 μm, and more preferably less than less than 10 pm.
    The resins used during the mixing in step a) above and which are present in the mixture of zeolitic particles according to the invention are advantageously chosen from polymers and, in this case, the preferred polymers are those obtained by an emulsion polymerization process and are in the form of a small discrete particle size, generally ranging from 1 nm to 100 μm, preferably from 1 nm to 50 μm, more preferably from 1 nm to 20 μm.
    In the mixture according to the present invention, obtained in step a) in the above process, the ratio between the particle sizes [(size of the resin particles) on (size of the zeolite particles)] is preferably 1: 20,000 to 3: 1, preferably 1:10,000 to 2.5: 1, more preferably 1: 1,000 to 2: 1.
    It should be noted that steps b), c), d) and e) can be performed in any order, concomitantly, one or two or more of these steps, or all of these steps, at the same time. one or more steps. A preferred embodiment comprises steps b), c), d) and e), one after the other. Step f) comprises the constant maintenance of the temperature and the pressure for a period of time generally between 1 second and 5 hours, preferably between 1 second and 1 hour. Step f) may also be optional in the process of the present invention.
    The temperature of the extruder or compression molding die must be high enough to soften the resin and allow the resin to adhere to the zeolite particles, typically about 5 to 10 ° C above the resin. melting point or the softening temperature of the resin. By way of nonlimiting example, for semi-crystalline polymers, the melting temperature generally reaches a minimum of 5 ° C. above the melting point of the crystallites of the polymers. For amorphous polymers, the temperature generally reaches 5 ° C above the softening temperature of the resin.
    A pressure is applied during step e). Typical pressures can be from 15 psi (0.1 MPa) to 2500 psi (17 MPa), typically from 435 psi (3 MPa) to 2500 psi (17 MPa) depending on the desired end properties.
    When the article reaches a suitable hardness, it can be extracted from the mold or extruded from the die. The appropriate hardness depends on the chosen resin. For semi-crystalline polymers, it is obtained at 5 ° C or higher below the primary recrystallization temperature, which is the point where crystalline phases can be measured. For amorphous polymers, it is obtained at 5 ° C or more below the hardness temperature where the glass transition of the polymer takes place.
    The article may have various forms, e.g. ex. selected from cubes, parallelepipeds, spheres, sheets, pleated sheets, films, pleated films, cylinders, convex regular polyhedra, prisms, cones, ellipses, pyramids, diamond-shaped patterns wave, propellers and the like.
    The article of the present invention, in its various forms as listed above, may also include various features used to increase the area, e.g. ex. protuberances (cones, cylinders, concentric circles, fins, support fins, and the like), bores (tapered and non-tapered bores, partial and through bores, which may include cross-sectional shapes such as circles, polygons, stars ), see p. ex. WO 2014/055546. The article may also include various channels, which may be circular, polyhedral or sinusoidal in nature.
    The various forms as defined above allow better control of the pressure drop in the article of the present invention, and thus reduce the energy consumption of purification / separation processes using the article of the invention. present invention.
    The article of the present invention thus allows the complete immobilization of the sorbent particles, which avoids the abrasion of the particles together and extends the period of usefulness of the article.
    According to another embodiment, the article has a mechanical strength, expressed as a compressive strength, ranging from 290 psi (2 MPa) to 14,500 psi (100 MPa).
    The article of the present invention provides adsorption and desorption kinetics good to excellent as required in several applications.
    Another aspect of the present invention relates to a method for separating a fluid from one or more other fluids and / or separating a fluid from impurities contained in said fluid, comprising the step of in contact with said fluid with at least one article as previously described herein.
    The invention also relates to the use of the adsorbent article as described above for drying, conditioning, purification and separation of gases, liquids and vapors. The adsorbent articles thus used can be regenerated by pressure swing adsorption processes, by heat treatment or by cleaning with solvents, and then drying.
    The articles according to the invention can be used for the drying of compressed air for applications such as air braking systems. The articles according to the invention can moreover be used in the refrigerant drying. The articles according to the invention can also be used for drying and desulphurizing liquid hydrocarbons, for drying and sweetening natural gas or for drying chemicals such as for example alcohols or for drying products. petrochemicals, for example cracked gas.
    Another application of the articles according to the invention may also include the separation of air in air separation units, in which nitrogen is adsorbed and the air is enriched with oxygen, e.g. ex. in units of breathing air. The articles according to the invention can also be used in air conditioning units for drying the refrigerant.
    The articles according to the invention may also be used for the purification of air before cryogenic distillation, for the removal of CO2 from air or different natural or synthetic gases.
    Finally, the shaped bodies according to the invention can be used as ion exchangers in water softening units, the desired effect being obtained by a calcium-sodium exchange.
    FIG. 1 is a cross-sectional representation of an example of an article (A) according to the present invention: the article comprises zeolitic particles (1), with at least one zeolitic adsorbent, said particles being immobilized with at least one resin (2).
    Such an article (A) is illustrated in Figure 2, which is a cross-sectional representation of an exemplary adsorbent cartridge (B). The cartridge (B) is an assembly of an article (A), which is inserted into a tub (6) (made of polymer or metal such as aluminum), comprising a seal casing (7) between the article and the wall of the vessel, to prevent ducting at the wall so that the fluid is forced through the article, and bearing caps (3, 3 ') tightly held by screws (4). and with seals (5) (O-rings shown). The flow at the inlet (10) is distributed in the flow distribution section (8) and the filter (9). The purified or separated flow is produced at the outlet (11). [0057] Fig. 3 is a cross-sectional representation of another example of a cartridge (C) using the article (A). The article is directly attached to the container vessel (14) through the resin (2), thus avoiding any channeling so that the fluid is forced through the article. Caps (13, 13 ') are sealed to the bowl (14) and the flow distribution section (12). The flow at the inlet (10) is distributed in the flow distribution section (12). The purified or separated flow is produced at the outlet (11).
    Figure 4 is a cross-sectional representation of an example of a cartridge (D) using article (A). The cartridge (D) is an assembly of an article (A), which is inserted into a vessel (15) (made of polymer or metal such as aluminum), and caps (14) tightly held by screws (4). ). The flow at the inlet (10) is distributed from an axial flow to a radial flow. The purified or separated flow is produced at the outlet (11) from a radial flow to an axial flow.
    Figure 5 is an SEM image of the dry formulation mixture obtained in step a) of the process as previously described, i.e. prior to immobilization by the compression molding process. The blend consists of 88% by weight of CECA Siliporite® Nitroxy® SXSDM beads and 12% by weight of Arkema's Kyblock ™ FG-81 resin. The SEM image is obtained by coating a thin layer of iridium using an ion beam coating device from Southbay Technologies, model IBSe. SEM images are obtained with a Hitachi SU8010 field emission SEM. This image shows the compatibility of a fully dispersed coating of Kyblock ™ FG-81 resin on the surface of Siliporite® Nitroxy® SXSDM beads.
    Figure 6 is an SEM image of another example of a dry formulation mixture obtained in step a) of the process as previously described, i.e. prior to immobilization by the compression molding process, without inorganic resin. The blend consists of 88% by weight of CECA Siliporite® NK30 zeolite powder and 12% by weight of Arkema Kyblock ™ FG81 resin. The SEM image is obtained by coating a thin layer of iridium using an ion beam coating device from Southbay Technologies, model IBSe. SEM images are obtained with a Hitachi SU8010 field emission SEM. This image shows the compatibility of a completely dispersed coating of Kyblock ™ FG-81 resin on the surface of the Siliporite® NK30 zeolite powder.
    The invention will be further illustrated by the following examples which are not intended to limit the scope of protection sought as indicated by the appended claims.
    EXAMPLE 1 is a compression molded cylindrical adsorbent article according to the invention consisting of 80% by weight of CECA Siliporite® Nitroxy® SXSDM beads and 20% by weight of Kyblock ™ FG-81 resin. Arkema. The article of Example 1 has a high bulk density and excellent mechanical integrity. To manufacture this article, the 20% by weight of the Arkema Kyblock ™ FG-81 resin is added to the 80% by weight of CECA Siliporite® Nitroxy® SXSDM beads. The two components are manually mixed into a homogeneous blend using a low shear friction technique in a mixing bowl equipped with a synthetic mixing blade for 15 minutes until the binary mixture becomes homogeneous. During mixing, the shaping die is preheated in an oven at 180 ° C. When the forming die reaches an equilibrium temperature of 180 ° C, the mixture is added to the 5.42 cm diameter forming die and compressed to 87 psi (0.6 MPa) for 1 minute. The article is then manually removed and placed in the preheated oven at 180 ° C for 5 minutes to fully cure the article. The article is then removed and allowed to cool to room temperature in a closed vessel to prevent adsorption of moisture through the article. The final article has dimensions of 5.42 cm in diameter by 3.95 cm in height.
    Example 2 is a compression molded cylindrical adsorbent article consisting of 95% by weight of CECA Siliporite® Nitroxy® SXSDM beads and 5% by weight of Arkema's Kyblock ™ FG-81 resin. The article of Example 2 has a high bulk density and excellent mechanical integrity. To make this part, the 5% by weight of Arkema's Kyblock ™ FG-81 resin is added to the 95% by weight of CECA Siliporite® Nitroxy® SXSDM beads.
    The two components are manually mixed into a homogeneous mixture using a low shear friction technique in a mixing bowl provided with a synthetic mixing blade for 15 minutes until the binary mixture becomes homogeneous. During mixing, the shaping die is preheated in an oven at 180 ° C. When the forming die reaches an equilibrium temperature of 180 ° C, the mixture is added to the 5.42 cm diameter forming die and compressed to 87 psi (0.6 MPa) for 1 minute. The article is then manually removed and placed in the preheated oven at 180 ° C for 5 minutes to fully cure the article. The article is then removed and allowed to cool to room temperature in a closed vessel to prevent adsorption of moisture through the article. The final article has dimensions of 5.42 cm in diameter by 3.59 cm in height.
    Characterization Techniques Average Particle Size [0065] The average particle size of the zeolitic particles present in the article is the number average of the largest dimension of the zeolitic particles observed by scanning electron microscopy (SEM).
    Several photographs of polished cross-sections prepared by ionic polishing are taken with an enlargement of at least 50. The largest dimension of at least 200 zeolitic particles is measured by means of specialized software, such as for example ImageJ ( http://www.imagej.net). The accuracy is about ± 3%.
    Mechanical properties: compressive strength and abrasion resistance [0067] Compressive strength: to determine the compressive strength of the article of the invention, a Zwick tensile / pressure tester, model UP 1455, is used. For this, cylindrical articles with a sample diameter of 5 mm are cut to a sample length of 7 mm. For exact and reproducible measurements of compressive strength, it must be ensured that the front faces of the article are flat and parallel. The measurement is performed at room temperature. The preliminary force is 1 N. The experiments are carried out at a test speed of 1 mm / min. The test force acts on the front faces.
    Abrasion resistance: a wet abrasion test is carried out under the following conditions: 136 ml of cylindrical articles with a sample diameter of 5 mm and a sample length of 7.5 mm are placed in a cylindrical container of 150 ml having a diameter of 4.4 cm and a height of 10 cm. 68 ml of ethanol are added, the container is closed and subjected to a high frequency vortex motion in a Model No. 30 Red Devil Paint Conditioner for 30 minutes. The fines produced by the abrasion are measured: the fines are then extracted from the articles by washing with ethanol through a standard sieve of 1.25 mm in a beaker and isolated from ethanol, brought to 80 ° C to dry fines and weighs. The weight obtained is expressed as a percentage by weight of the initial charge.
    权利要求:
    Claims (15)
    [1" id="c-fr-0001]
    An adsorbent article comprising zeolitic particles of at least one zeolitic adsorbent, said particles being immobilized with at least one resin, the average particle size of said at least one zeolitic adsorbent ranging from 0.03 mm to 3 mm, preferably from 0.04 mm to 2 mm, more preferably 0.05 mm to 1 mm, and the zeolite content being greater than or equal to 60% by weight, the zeolite content being more preferably greater than 70% by weight. weight, preferably strictly greater than 80% by weight, more preferably strictly greater than 85% by weight, even more preferably strictly greater than 88% by weight, generally greater than or equal to 90% by weight, relative to total weight of said article.
    [2" id="c-fr-0002]
    An article according to claim 1, wherein the zeolitic particles have various shapes, for example beads, pellets, extrudates, crushed marbles, crushed pellets, flakes, cracked products, and in general all types of shapes, rounded or not, hollow or not, such as cenospheres, and the like, and / or mixtures thereof.
    [3" id="c-fr-0003]
    An article according to claim 1 or claim 2, wherein at least one zeolitic particle in said article has a dimension greater than or equal to 0.1 mm.
    [4" id="c-fr-0004]
    An article according to any one of claims 1 to 3, wherein the zeolitic particles in the article comprise at least one zeolitic adsorbent in the form of one or more zeolites agglomerated with one or more inorganic binders, such as natural clays, synthetic clays, silica, alumina and the like, preferably natural clays and / or synthetic clays, more preferably natural clays.
    [5" id="c-fr-0005]
    5. Article according to any one of claims 1 to 4, wherein said zeolitic particles comprise at least one zeolite or a mixture of zeolites, which are advantageously chosen from zeolites A (LTA type frame), chabazite (framework of type CHA), clinoptilolite (HEU type frame), ΙΈΜΤ (EMT type frame), ZSM-5 (MFI type frame), silicalite-1 (MFI type frame) and faujasite (FAU type frame) ), and more preferably among the FAU type zeolites.
    [6" id="c-fr-0006]
    6. Article according to claim 5, wherein the FAU type zeolites are selected from X zeolites, MSX zeolites, LSX zeolites and Y zeolites, as well as mixtures of two or more of them in all proportions.
    [7" id="c-fr-0007]
    7. Article according to any one of claims 1 to 6, wherein the zeolitic particles contain an inorganic binder, said inorganic binder being selected from kaolins, kaolinites, nacrites, dickites, halloysites, attapulgites, sepiolites , delaminated clays (eg in the form of gels), montmoroniites, bentonites, illites and metakaolins, as well as mixtures of two or more of them in all proportions.
    [8" id="c-fr-0008]
    8. Article according to any one of claims 1 to 7, wherein said at least one resin comprises polymers, in particular thermoplastic homo- and / or copolymers and also polycondensates, non-limiting examples of polymers being polyolefins, in particular low and / or high and / or ultra-high density polyethylene, polypropylene, ethylene copolymers, ethylene-vinyl acetate copolymers, polyacrylics, acrylonitrile homo- and / or copolymers, polyacrylates polymethacrylates, acrylate copolymers and / or methacrylate copolymers, polystyrenes and / or styrene copolymers, polyesters, e.g. ex. polyethylene terephthalate, polybutylene terephthalate, halogenated polymers and copolymers such as polyvinylidene difluoride (PVDF) polymers, polymers and / or copolymers of polytetrafluoroethylene (PTFE), polyamides, such as polyamide And polyamide-12, as well as other even and odd polyamides, aromatic polyamides, polyvinyl chlorides, polyurethanes, polyethersulfones, polyetherketones, polycarbonates, epoxy resins, phenolic resins, thermosetting resins and elastomeric resins, and the like, and mixtures thereof.
    [9" id="c-fr-0009]
    9. Article according to any one of claims 1 to 8, the content of active material (ie adsorbent material), expressed as the weight content of zeolite relative to the total weight of said article, is greater than or equal to 60% by weight, preferably greater than 70% by weight, more preferably strictly greater than 80% by weight, even more preferably strictly greater than 85% by weight, even more preferably strictly greater at 88% by weight, generally greater than or equal to 90% by weight.
    [10" id="c-fr-0010]
    10. Article according to any one of claims 1 to 9, whose shape is chosen from cubes, parallelepipeds, spheres, sheets, pleated sheets, films, pleated films, cylinders, convex regular polyhedra. prisms, cones, ellipses, pyramids, wave-shaped patterns, propellers, and the like.
    [11" id="c-fr-0011]
    11. Article according to any one of claims 1 to 10, which comprises various features used to increase the area, e.g. ex. protuberances (such as cones, cylinders, concentric circles, fins, support fins, and the like), bores (tapered and non-tapered bores, partial and through bores, which may include cross-sectional shapes such as circles, polygons , stars).
    [12" id="c-fr-0012]
    12. Article according to any one of claims 1 to 11, which comprises various channels, which may be of circular, polyhedral or sinusoidal nature.
    [13" id="c-fr-0013]
    An article according to any one of claims 1 to 12, having a strength, expressed as compressive strength, ranging from 290 psi (2 MPa) to 14,500 psi (100 MPa).
    [14" id="c-fr-0014]
    A method of separating a fluid from one or more other fluids and / or separating a fluid from impurities contained in said fluid, comprising the step of contacting said fluid with at least one article according to any of claims 1 to 13.
    [15" id="c-fr-0015]
    15. The method of claim 14 for drying, conditioning, purification and separation of gases, liquids and vapors.
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    同族专利:
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    JP6714023B2|2020-06-24|
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    KR20180026514A|2018-03-12|
    PL3317010T3|2021-12-13|
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    ZA201708476B|2019-06-26|
    US10464042B2|2019-11-05|
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    法律状态:
    2016-06-13| PLFP| Fee payment|Year of fee payment: 2 |
    2017-01-06| PLSC| Publication of the preliminary search report|Effective date: 20170106 |
    2017-06-13| PLFP| Fee payment|Year of fee payment: 3 |
    2017-10-27| TP| Transmission of property|Owner name: ARKEMA FRANCE, FR Effective date: 20170922 |
    2018-06-12| PLFP| Fee payment|Year of fee payment: 4 |
    2019-06-19| PLFP| Fee payment|Year of fee payment: 5 |
    2020-06-12| PLFP| Fee payment|Year of fee payment: 6 |
    2021-06-11| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1556246|2015-07-02|
    FR1556246A|FR3038240B1|2015-07-02|2015-07-02|ARTICLE COMPRISING ZEOLITIC PARTICLES CONNECTED WITH A RESIN|FR1556246A| FR3038240B1|2015-07-02|2015-07-02|ARTICLE COMPRISING ZEOLITIC PARTICLES CONNECTED WITH A RESIN|
    PCT/IB2016/001101| WO2017001935A1|2015-07-02|2016-07-01|Article with zeolitic particles bonded with resin|
    ES16770542T| ES2890875T3|2015-07-02|2016-07-01|Article with resin-bonded zeolitic particles|
    US15/738,424| US10464042B2|2015-07-02|2016-07-01|Article with zeolitic particles bonded with resin|
    PL16770542T| PL3317010T3|2015-07-02|2016-07-01|Article with zeolitic particles bonded with resin|
    EP16770542.5A| EP3317010B1|2015-07-02|2016-07-01|Article with zeolitic particles bonded with resin|
    JP2017568158A| JP6714023B2|2015-07-02|2016-07-01|Articles with zeolite particles bound by resin|
    CN201680038950.0A| CN108025280B|2015-07-02|2016-07-01|Article having zeolite particles bound with resin|
    KR1020187003378A| KR102110056B1|2015-07-02|2016-07-01|Articles with zeolite particles bound to the resin|
    ZA2017/08476A| ZA201708476B|2015-07-02|2017-12-13|Article with zeolitic particles bonded with resin|
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